Sulfinyl thiol- and dithio-phosphates

ABSTRACT

SULFINYL THIOL-AND DITHIO-PHOSPHATES, I.E. O,O-DIALKYLS-(TRICHLOROETHYL AND DICHLOROVINYL SULFINYL)-THIOL-AND DITHIO-PHOSPHATES, OR O,O-DIALKYL-S-(TRICHLOROETHYL THIONYL AND DICHLOROVINYL THIONYL) THIOL-AND THIONOTHIOLPHOSPHATES, WHICH POSSES STRONG FUNGICIDAL, NEMATOCIDAL AND INSECTICIDAL PROPERTIES AND WHICH MAY BE PRODUCED BY CONVENTIONAL METHODS.

United States Patent 3,629,375 SULFINYL THIOL- AND DITHIO-PHOSPHATESPaul C. Aichenegg, Prairie Village, Kans., and Richard A. Thornhill,Kansas City, Mo., assignors to Chemagro Corporation, Kansas City, M0.

N0 Drawing. Filed Mar. 4, 1969, Ser. No. 804,272 Int. Cl. C071? 9/16;A01n 9/36 US. Cl. 260-934 12 Claims ABSTRACT OF THE DISCLOSURE Snlfinylthioland dithio-phosphates, i.e. 0,0-dialkyl- S-(trichloroethyl anddichlorovinyl sulfinyD-thioland dithio-phosphates, or0,0-dialkyl-S-(trichloroethyl thionyl and dichlorovinyl thionyl)thioland thionothiolphosphates, which possess strong fungicidal,nematocidal and insecticidal properties and which may be produced 'byconventional methods.

The present invention relates to and has for its objects the provisionfor particular new sulfinyl thioland dithiophosphates, i.e.0,0-dialkyl-S-(trichloroethyl and dichlorovinyl sulfinyl)-thiolanddithio-phosphates, or 0,0- dialkyl-S-(tricholoethyl thionyl anddichlorovinyl thionyl) thioland thionothiol-phosphates, which possessvaluable pesticidal, especially fungicidal, nematocidal andinsecticidal, properties, active compositions in the form of mixtures ofsuch compounds with solid and liquid dispersible carrier vehicles, andmethods for producing such compounds and for using such compounds in anew way, especially for combating fungal diseases, nematodeinfestations, and insect pests and the like, with other and furtherobjects becoming apparent from a study of the within specification andaccompanying examples.

It is not believed that any sulfinyl thioland/ or dithiophosphates ofanalogous constitution are known and/or are known to possess combinedfungicidal, nematocidal and insecticidal properties.

It has now been found, in accordance with the present invention, thatthe particular new sulfinyl thioland dithio-phosphates of the generalformula 0 (RO) ]t S- R' in which:

R is alkyl of 1-4 carbon atoms, R is trichloroethyl or dichlorovinyl,especially having at most one oL-ChlOIO group, and X is oxygen orsulfur,

exhibit strong fungicidal, nematocidal and insecticidal properties.

It has been furthermore found, in accordance with the present invention,that the compounds of Formula 1 above may be produced by a process whichcomprises (a) Reacting a thiolor dithio-phosphoric acid ester of theformula in which R and X are the same as defined above, withtrichloroethyl or dichlorovinyl sulfinyl chloride of the respectiveformulae in which correspondingly one Y' is chlorine and the other Y ishydrogen, optionally in the presence of a solvent, or

3,629,375 Patented Dec. 21, 1971 "Ice in which R, X and Y are the sameas defined above, with a dehydrochlorinating agent in the presence of asolvent.

Suprisingly, the sulfinyl thioland dithio-phosphates of the instantinvention are chemically completely novel compounds unobvious over theprior art. Because of their combined fungicidal, nematocidal andinsecticidal properties and their broad spectrum of activity, theinstant compounds therefore represent a valuable enrichment of the art.

According to reaction variant (a), if for instance 2,2- dichlorovinylsulfinyl chloride (IVa) and 0,0-dimethyl dithiophosphoric acid ('IIa)are used as starting materials, the course of the reaction can berepresented by the following equation:

(Ila) (IVa) According to reaction variant (b), the corresponding vinylsulfinyl thioland dithio-phosphates of Formula I, i.c. in which R isvinyl, may alternatively be obtained by dehydrochlorinating thetrichloroethyl sulfinyl thiolor dithio-phosphate of Formula 1i in thepresence of a dehydrochlorinating agent such as tertiary amine or analkoxide, according to the following equation:

Advantageously, in accordance with the present invention, in the variousformulae herein,

R represents lower alkyl hydrocarbon of 1-4 carbon atoms, such asmethyl, ethyl, n-propyl, isopropyl, nbutyl, isobutyl, sec.-butyl,tert.-butyl, and the like, especially C or C alkyl, and more especiallymethyl and ethyl;

R represents trichloroethyl, preferably having at least one terminal orfi-chloro group, i.e. at most one chloro group in inc-position to theadjacent sulfinyl group, such as 2,2,2- and 1,2,2-trichloro ethyl; ordichlorovinyl, i.e. having at least one terminal or S-chloro group, i.e.at most one chloro group in a-pOSitiOH to the adjacent sulfinyl group,such as 2,2- and 1,2-dichlorovinyl; and

X represents oxygen; or sulfur.

Preferably, R is C alkyl, R is trichloroethyl or dichlorovinyl and X isoxygen or sulfur, both symbols R being the same.

Furthermore, especially where R is C alkyl, R is preferably2,2,2-trichl'oroet1hyl when X is oxygen or sulfur; or R is preferably1,2,2-trichloroethyl when X is oxygen or sulfur, or R is preferably2,2-dichlorovinyl when X is oxygen or sulfur; or R is preferably1,2-dichlorovinyl when X is oxygen or sulfur.

:Preferred compounds include:

(9) 0,0-dimethyl-'S- (2,2-dichlorovinyl-sulfinyl) thiolphosphate;

( 14) O, O-dimethyl-S-( l,2,Z-trichloroethyl-sulfinyl dithio-phosphate;

(8) O,'O-dimethyl-S-(1,Z-dichlorovinyl-sulfinyl)-thiolphosphate;

( 1'0) 0,0-diethyl-S-( 1,2,2-trichloroethyl-sulfinyl) -dithiophosphate;

(3 0,0-diethyl-S- (2,2,2-trichloroethyl-sulfinyl) -thiol phosphate;

(4) 0,0-diethyl-S-( 1,Z-dichlorovinyl-sulfinyl) -thiolphosphate;

( l l 0,0-diethyl-S- (2,2,2-trichloroethyl-sulfinyl -dithiophosphate;and

( 16) O, O-dimethyl-S-( 1,2-dichlorovinyl-sulfinyl -dithiophosphate.

The types of thioland dithio-phosphoric acid esters usable as startingmaterials in accordance with process variant (a) of the presentinvention are clearly characterized by Formula II noted above.

These 0,0-dialkyl-thioland dithio-phosphoric acid esters are Well knownand can be prepared on an industrial scale:

As examples of such thioland dithio-phosphoric acid esters which can beused as starting materials for process variant (a) according to thepresent invention; there may be mentioned in particular:

-0,0-dimethyl-thio phosphoric acid, 0,0-dimethyl-dithio-phosphoric acid,0,0-diethyl-dithio-phosphoric acid, 0,0-diethyl-thiol-phosphoric acid,O,O-diisopropyl-dithio-phosphoric acid, O,O-di-n-butyl-thiol-phosphoricacid, 0,0-di-sec.-butyl-dithio-phosphoric acid, and the like.

The types of trichloroethyl and dichlorovinyl sulfinyl chlorides usableas starting materials in accordance with process variant (a) of thepresent invention are clearly characterized by Formulae III and IV notedabove.

These sulfinyl chlorides may be prepared by reacting the correspondingsulfenyl chlorides in acetic acid with an excess of chlorine at atemperature not exceeding 7 C. during the chlorine addition. Thereaction mixture is then a llowed to warm up to room temperature and tostand overnight. The mixture is then heated to 65-75 C. for one hour,volatiles are stripped off and the product fractionated in high vacuum.

Another mode of preparation of these starting sulfinyl chlorides thatcan be used with advantage for process variant (a) is that as describedby I. Douglass, 1.0.0. 33, 21-05, 1968, which requires the use of thecorresponding disulfides as starting materials in place of the sulfenylchlorides.

The starting trichloroethyl and dichlorovinyl sulfenyl chlorides usablefor process variant (a) may also be prepared from the correspondingdisulfides as described in US. Pat. No. 3,293,304.

As examples of such sulfinyl chlorides which can be used as startingmaterials for process variant (a) according to the present inventionthere may be mentioned in particular:

1,2,2-trichloroethyl sulfinyl chloride, 2,2,2-trich'loroethyl sulfinylchloride, 1,2-dichlorovinyl sulfinyl chloride, and 2,2-dichlorovinylsulfinyl chloride.

In addition to the reagents employed, the reaction according to processvariant (a) may be carried out optionally in the presence of an inertorganic solvent (this term also includes a mere diluent). Examples ofsuch solvents include hydrocarbons such as petroleum ether, hexane,benzene, toluene and chlorinated hydrocarbons such as methylenechloride, dichloroethane, chloroform,

carbon tetrachloride, chlorobenzene, dichlorobenzene, and the like; butthe preferred solvents are chloroform or carbon tetrachloride. Othersolvents such as ethers (tetrahydrofuran, diethyl ether, dioxane),esters (ethyl ace tate) or ketones (acetone, cyclohexanone), and thelike, have been found to result in decreased yields of the subjectcompounds but are still usable despite this disadvantage.

The reaction temperature for process variant (a) can be varied within afairly wide range. In general, the reaction is carried out atsubstantially between about 20- 150 C., preferably between about 50-l00C.

In general, for process variant (a), the reactants are used inapproximately equimolar proportions or an excess of the thiol or dithiophosphoric acid ester of Formula II may be used with advantage. Thelatter can be removed by washing the obtained crude reaction mixturewith water. The reaction can for example be carried out in such a mannerthat the sulfinyl chloride of Formula III or IV is added dropwise to asolution or suspension of the thiol or dithio phosphoric acid ester atroom temperature (25 C.) allowing the temperature to rise (exothermicreaction), and keeping the reaction mixture at between 50 and C. untilthe evolution of hydrogen chloride has ended.

Furthermore, in connection with the final work-up according to processvariant (a), washing with water, drying of the organic solution overMgSO and evaporating the solvent yields the corresponding sulfinylthiophosphate of Formula I in pure form.

For process variant (b) the preferred dehydrochlorinating agent used istriethylamine in an inert organic solvent such as petroleum ether, butalkali, i.e. alkali metal alkanolate such as sodium ethoxide in ethylalcohol or the like as solvent, can also be used successfully.

In general, for process variant (b), an equimolar amount of thedehydrochlorinating agent, i.e. base, is added to the trichloroethylsulfinyl thiolor dithio-phosphate at between 25 and 50 C. and thereaction mixture held at temperatures ranging from 50-100 C. until theformation of the base hydrochloride, e.g. amine hydrochloride or sodiumchloride, respectively, has ended.

For the final work-up according to process variant (b), filtration,washing with water, drying of the organic solution over MgSO and highvacuum evaporation of the solvent used yields the corresponding vinylsulfinyl phosphate in pure form.

Advantageously, the active compounds according to the present inventionexhibit strong fungicidal, nematocidal and insecticidal properties withcomparatively low toxicity to warm-blooded creatures and concomitantly10w phytotoxicity. Hence, the instant compounds are suitable for use asplant protection agents, and in the hygiene field, for the control offungi, nematodes and insects.

As to the fungicidal properties, the instant compounds possess a broadspectrum of activity.

Thus, the instant compounds can be used for the control of fungi fromthe most widely different classes of fungi, such as for exampleArchimycetes, Phycomycetes, Ascomycetes, Basidiomycetes, Fungiimperfecti, and the like. The instant compounds can give particularlyeffective results against parasitic fungi on above-ground parts ofplants, fungi causing tracheomycosis, which attack the plant from thesoil, seed-borne fungi, and soilborne fungi, such as the organismsCeratocyszis ulmi, Colletotrichum obiculare, F usarz'um lycopersici, Fusarium nivale, Helminthosporium satirum, Rhizoctonia solani,Verticillium alboatrum, Pythium, Alternaria, Ustilago, and the like.

As to the nematocidal properties, the instant compounds have outstandingactivity. Thus, the instant compounds can also be used for the controlof nematodes of the saprophytic type Panagrellus and Rhabditis ssp., andthe like.

As to the insecticidal properties, the insecticidal action sets inrapidly and is long-lasting.

Thus, the instant compounds can furthermore be used with very favorableresults for the control of noxious biting insects and Diptera.

With the biting insects contemplated herein there are classed, in themain, beetles, such as the confused flour beetle (Tribolium confusum).

The Diptera contemplated herein comprise in particular flies, such asthe housefly (M usca domestica).

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert pesticidal diluents or extenders, i.e. conventionalpesticidal dispersible carrier vehicles, such as solutions, emulsions,suspensions, emulsifiable concentrates, spray powders, pastes, solublepowders, dusting agents, granules, etc. These are prepared in knownmanner, for instance by extending the active compounds with conventionalpesticidal dispersible liquid diluent carriers and/or dispersible solidcarriers optionally with the use of carrier vehicle assistants, e.g.conventional pesticidal surfaceactive agents, including emulsifyingagents and/ or dispersing agents, whereby, for example, in the casewhere water is used as diluent, organic solvents may be added asauxiliary solvents. The following may be chiefly considered for use asconventional carrier vehicles for this purpose: Inert dispersible liquiddiluent carriers including inert organic solvents, such as aromatichydrocarbons (e.g. benzene, toluene, xylene, etc.), halogenated,especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes,etc.), paraffins (e.g. petroleum fractions), chlorinated aliphatichydrocarbons (e.g. methylene chloride, etc.), alcohol (e.g. methanol,ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine, etc.),ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.), amides(e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide,etc.), ketones (e.g. acetone, etc.), and/or water; as well as inertdispersible finely divided solid carriers, such as ground naturalminerals (e.g. kaolins, alumina, silica, chalk, i.e. calcium carbonate,talc, kieselguhr, etc.) and ground synthetic minerals (e.g. highlydispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereasthe following may be chiefiy considered for use as conventional carriervehicle assistants, e.g. surface-active agents, for this purpose:emulsifying agents, such as non-ionic and/ or anionic emulsifying agents(e.g. polyethylene oxide esters of fatty acids, polyethylene oxideethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., andespecially alkyl arylpolyglycol ethers, magnesium stearate, sodiumoleate, etc.); and/or dispersing agents, such as lignin, sulfite wasteliquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/ or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other fungicides,insecticides or nematocides, or herbicides, bactericides, etc., ifdesired, or in the form of particular dosage preparations for specificapplication made therefrom, such as solutions, emulsions, suspensions,powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 0.195%, and preferably0.5- 90%, by Weight of the mixture, whereas carrier composition mixturessuitable for direct application or field application generallycontemplate those in which the active compound is present in an amountsubstantially between about 0.000l2.0%, preferably 0.0l-0.8%, by weightof the mixture. Thus, the present invention contemplates overallcompositions which comprise mixtures of a conventional dispersiblecarrier vehicle such as (l) a dispersible inert finely divided carriersolid and/or (2) a dispersible carrier liquid such as an inert organicsolvent and/or water preferably including a surface-active effectiveamount of a carrier vehicle assistant, e.g. surface-active agent, suchas an emulsifying agent and/or a dispersing agent, and an amount of theactive compound which is effective for the purpose in question and whichis generally between about 0.000 l-%, and preferably 0.01-95%, by weightof the mixture.

The active compound can also be used in accordance with the well-knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment in finelydivided form, e.g. average particle diameter of from 50- microns, oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 1 quart/acre, preferably 2-16 fluidounces/ acre, are sufiicient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about 20 to about 95% by weight, of the activecompound, or even the 100% active substance alone, e.g. about 20-100% byweight of the active compound.

Furthermore, the present invention contemplates methods of selectivelykilling, controlling or combating pests, i.e. fungi, nematodes and/orinsects, which comprise applying to at least one of (a) such fungi, (b)such nematodies, (c) such insects, and (d) the corresponding habitat,i.e. the locus to be protected. a correspondingly pesticidally toxicamount, i.e. a fungicidally, nematocidally and/ or insecticidallyeffective amount, of the particular active compound of the inventionalone or together with a carrier vehicle as noted above. The instantformulations or compositions are applied in the usual manner, forinstance by spraying, atomizing, vaporizing, scattering, dusting,watering, sprinkling, pouring, and the like.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application, and may be varied within a fairlywide range, depending upon the weather conditions, the purpose for whichthe active compound is used, and the type locus to be treated.Therefore, in special cases, it is possible to go above or below theaforementioned concentration ranges.

In commercial practice, the compositions when used as fungicides andnematocides according to the present invention are usually applied tothe soil infected with fungi and nematodes.

The outstanding fungicidal, nematocidal and insecticidal activity of theparticular active compounds of the present invention is illustrated,without limitation, by the following examples.

'EXAMPLE 1.FUNGICIDAL ACTIVITY Agar plate fungicide test [myceliumgrowth] Solvent: Parts by wt.

Distilled Water 99 Dispersing agent:

Polyoxyethylene sorbitane monolaurate (Tween To product a suitablepreparation of the particular "active 'compound,"1 part by weight ofsuch active com- When the mixture of substrate and active compound hassolidified, the dishes are inoculated in the center of the plate withthe species of gungi stated in the table and incubated at roomtemperature (21-25" C.) for 7 days.

' After this time, the extent of mycelial growth is determined torelation to the growth of the untreated control by measuring the averageradius of the fungal colony from the central point of inoculation to theperiphery of mycelial growth. The inhibition of fungal growth isexpressed by the values to 10, wherein 0 means that there is noinhibition (full growth as in control and means that there is completeinhibition (absence of growth).

The particular active compounds tested, there concentrations in the agarused, the test fungi and the inhibition effects achieved can be seenfrom the following Table 1:

To produce a suitable preparation of the particular active compound, 1part by weight of such active compound is mixed intimately with 1 partby weight of the stated wettable powder base.

Separate 0.1 and 0.025 part by weight portions, respectively, of theresulting mixture are blended in turn with 2 parts by Weight of clay(attapulgite) and 500 parts by weight of soil infected with the dampingoff organism (Pythium), to provide 2 corresponding soil portions. ThePythium infested soil is prepared by mixing thoroughly Pythium culturesfrom -30 agar plates with lbs. of steam-sterilized soil and adding 500ml. of pea seeds to maintain virulence.

After standing at room temperature for 24 hours, each said activecompound-containing soil portion is divided TABLE 1.AGAR PLATE FUNGICIDETEST Cone. Cerato- Oolletot- Fusarium Helminto- Verticilcystis riehumlyco- Fusarium sporium Rhizoctolium Pyth- Active compound p.p.n1. ulmiobiculare persiei nivale sativum nia solani alboatrum ium (2 O 500 10 1010 10 10 10 l0 10 II I! 100 10 0 5 2 10 10 5 5 (C2H O)zP-SSCHClOHOlz 108 0 2 0 5 10 2 5 (31) O O 500 10 8 10 5 10 10 II II 100 s 5 5 2 5 10(C2H50)zP-S-SCH2CC13 l0 2 0 5 0 0 10 (4 O O 500 5 10 10 5 l0 10 [1 100 28 l0 2 10 10 (CzH5O)zPSS-C Cl=OHC1 10 0 5 5 0 8 8 51) o o 500 s s 10 1o10 10 II II 100 5 5 10 10 5 5 (CzH50)zP-SS-CH=CC12 10 0 0 5 5 0 0 (6 O O500 10 10 10 10 10 10 I] II 100 8 5 l0 2 10 10 (CH O)2P-S-S-CHC1CHCI2 108 2 5 2 5 10 (7 O O 500 8 8 10 5 10 10 II II 100 5 2 s 2 5 10(OH30)2PSS-OH2CO13 10 2 0 0 0 5 0 (8 O O 500 10 10 10 10 10 10 II I] 10010 10 10 10 10 1o (CH O)2P-S-SCCl=CHCl 10 10 10 1O 10 10 10 (91) O O 5005 5 5 10 10 10 H II 100 2 2 2 2 0 5 (CH O)zPS--SCH=C C12 10 0 0 2 2 0 2(10 S O 500 10 10 10 10 10 10 10 10 II II 100 10 10 10 10 10 10 10 10(CzH5O)2P-SSCHC1CHCI2 10 10 10 10 10 10 10 10 5 (11 S O 500 5 2 10 5 105 ll H 100 5 0 5 2 5 2 (C2H O)2P-S-SCHzCCla 10 O 0 5 0 5 2 (121) S O 5008 5 5 2 8 10 II II 100 5 0 5 0 5 8 (C;H O)2PSSCCl=CI-IC1 2 o o 0 5 5(131) S O 500 10 10 10 1O 8 10 l! H 100 s s 10 1o 5 10 (C2H5O)2P-SCH=CC12 1O 5 5 5 1O 5 10 (14 S O 500 10 10 10 10 10 10 10 10 II I 100 1010 l0 10 10 10 10 10 (CH30)2PSSCHC1CHC13 10 10 10 10 10 8 10 10 5 S 0(151) I II 500 s s 10 10 10 10 10 s (CH O) P-S -CHzC C1 100 5 2 10 2 5l0 8 5 10 2 0 5 0 0 10 0 0 15, s s 500 10 10 1o 10 1o 10 I] I] 100 10 1010 10 10 10 (CH O)ZPS-SCCI=CHOI 10 10 10 10 10 10 10 (1;) S O 500 10 1010 10 10 10 II 100 10 1O 10 8 10 10 (CH O) PSSOH=CCl 10 10 10 10 2 10 1oEXAMPLE 2.FUNGICIDAL ACTIVITY Soil fungicide test ([rolled towel]Wettable powder base consisting of:

Hydrated silica (ultra fine, Hi-Sil 233) 92 Sodium lignin sulfonate(Marasperse N) 4 Polycondensate of ethylene oxide, propylene oxide andpropylene glycol (mol. wt. about (1000) (Pluronic L-61) Parts by 4complete control.

The particular active compounds tested, the amounts applied and theresults obtained can be seen from the following Table 2:

To produce a suitable preparation of the particular active compound, 1part by weight of such active compound is mixed intimately with l partby weight of the i TABLE 2 .S 0IL FUNGICIDE TEST [ROLLED TOWEL] Activecompound Control in concentrapercent of Active compound tion, p.p.m.Pythinm (0111 .0)2 SSCHC1CHC12 3 0 O 100 0 2) iL H 25 0 (02 60):-'-SS-CH2CCI3 (4g) O O 100 100 it Il 25 100 (021150): --SS-CC1=CHC1 (OM0): -SSCH=CCI2 O O 100 80 .62) g H I 25 5O (CHaO)2 S-SCHC1CHC12 (72) O O100 70 {i ll 25 (011 0 SSCH2CCI 8 O O 100 0 2) g H 25 0 (Cf-I3S-S-CC1=CHC1 (9g) O O 100 0 II II 25 0 (CH3O)2P--SSCH=CC12 (10;) S O 10090 g I! 25 70 (CzH)2 -SSCHC1CHCI;

(11 S O 100 {l g V 25 70 (C2H5O)2 S-\' CHz-CC13 (12 S O 100 0 it I] 25 0(621150): SSCC1=CHC1 1 S O 100 70 32) {l H 25 70 (CzHa0)2 SSCH=CCI1 (1'4S O 100 11 ll 25 so (CH 0)2 SSCHCl-CHC12 (15 S O 80 I {i ll 25 so(C1130): S-SCH2-CC13 16 S O 100 100 2) {L g 25 0 (011 0 S '-CC1=CHC1 1 SO 100 100 a) 11 g 25 0 t (CH;O)2 S -CH=CG12 EXAMPLE 3.NEMATOCIDAL ACTIONS aprophytic nematode Wettable powder base consisting of: 70 Theactivecompound preparation is added to a vial and i P Parts of wt. thena standard nematode suspension (i.e. 1 drop of 50-75 1 L ,r nematodes(Panagrellus and Rhabditis) per drop of active l f f (ultra H1 2 1' "192 compound preparation) is aded thereto. The vial is insodlum 1 3sulfonate v Maraperse N 4 cubated at room temperature (21-25 5 C.) for48 hours.

Polycondensate of ethylene oxide,lpropylene oxide and test [contactaction] propylene glycol (mol. wt. about 1000) (Pluronic L-61 statedwettable powder base, and the resulting mixture is diluted with water tothe desired final concentration.

75 The ability of the particplar active compound to immo- The particularactive compounds tested, their concentrations and the results obtainedcan be seen from the following Table 3:

TABLE 3.SAPROPHYTIC NEMATODE TEST [CONTACT ACTION] Immobili- Aetlvezation compound in percent con'cenof e a r tratlon, saprophytie Activecompound p.p.m. nematodes (23) 200 10 H H a 100 10(C2HaO)zP-S--SCHC1CHC1 3(5) 10 O 200 8 ll H 100 so (33)(C2H5O)2PSSCH2CC13 50 1 0 o 200 5o 100 (43) (CzHaO): SSCC1=CHC1 50 10 OO 200 100 II II 100 s0 (53). (c2H50)2P'SS-CH=C Ch 50 50 o 0 200 100 llII 100 80 (6a) (C1130); S- CHCl-CHC11 3g 5% 12.5 0

O O 200 100 I! II 100 s0 (01130 --SS-CH2CC1: gg 5g 12. 5 0

o o '200 100 II II 100 so (83) (CH:0)zPSS-CC1=CHQI 50 50 (9(CH30)zPSS-CH=CCI2 50 10 (10 0 200 80 II 100 50 (O;H O)zPS-S-CHC1CHC1:2( 5% (11 O 200 80 H II 100 50 (CgH50)zP-SSCH:CCI; 50 50 (12;) O 200 80I! II 100 50 (C2H 0)2Ps-SCO1=OHC1 60 50 (13a) S O 200 100 g H 100 50 (14S O 200 100 I! H 100 so (CHaO)zP-SSCHCI-CHCI1 50 50 (15 S O 200 50 i aIll [I r 100 30 (011 0); S- CHCC1 50 0 (16 O 200 100 II II 100 100(CH)zP-SSCC1=CHC1 100 (14) O 200 100 g g 100 100 of this time. Thenumber of non-motile'nematodes as corn- (T riboli um confusum) Solvent:10 milliliters ac etone;

EXAMPLE 4.-INSECTiCIDAL ACTION I I,

Confused flour beetle test [contact action] To produce a suitablepreparation of the particular active compound, mg. of such'activecompoundare mixed with the stated amount of the stated volatile solvent,and the resulting concentrate is diluted with further solvent to thedesired final concentration.

TABLE 4.-CONFUSED FLOUR BEETLE TEST [CONTACT ACTION] Amount of Flourbeetle moraetlve tality in percent compound after exposure ot applied inActive compound mmg./dish 2 hrs. 18 hrs.

(2 O 1, 000 100 100 g u 100 100 100 (C2H50)2 SSOHC1CHO11 10 0 0 (34) 0 01, 000 100 100 1|; I] 100 40 100 (G 0); SS-CH2CC1a 0 50 (CzH5O )2i S S-C CIT-GHQ].

(0 B 0 )2i S S CH=C C12 (64) 0 O 1, 000 100 100 {l [I 100 70 (OH3O)2-S-SCHCICHCI2 10 0 0 (7 O O 1, 000 100 100 II [I 100 90 100 (CH3O)2P-SCH1CC13 10 0 0 (84) O 1, 000 100 100 II II 100 100 100 (CH30)2PSS-CC1=CHO1 10 0 0 (94) O O 1, 000 100 100 {l H 100 100 100 (CH O)2S-SCH=CC12 10 0 0 (104) 0 1, 000 100 100 H I! 100 0 0(CzH5O)zP-SS-CHC1CHC12 10 0 0 (11 0 1, 000 90 100 II [I 100 0 o(CzH)zP-SSCHz-CC1; 1O 0 O (124) S O 1, 000 100 100 ll, II 100 o 100(0211 0); SSCC1=CHO1 10 0 0 (134) S O 1, 000 100 100 ll I] 100 0 30(CzH50)2 SS--CH=C C12 10 0 0 (144) S O 1, 000 100 100 ll It 100 20 0(011 0 SSCHC1CHO1 10 0 0 (154) S O 1, 000 100 100 1; II 100 0 0 (01130S-SCH2CCl3 10 0 0 (164) S O 1, 000 100 100 {1 II 100 20 30 (011 0);SSOC1=CHC1 10 0 0 (15) S 0 1, 000 100 it ll 100 e 0 (CHaO)2 S CH=CC12 100 0 NOTE-1 mmg.=0.000001 g.

EXAMPLE 5.INSECTICIDAL ACTION Housefiy test [contact action] (Muscadomestica) Solvent: 10 milliliters acetone.

To produce a suitable preparation of the particular active compound, mg.of such active compound are mixed with the stated amount of the statedvolatile solvent, and the resulting concentrate is diluted with furthersolvent to the desired final concentration.

One ml. of the resulting active compound preparation is placed into an8-ounce wide-mouth jar and an addiused and the results obtained can beseen from the foltional 4 ml. of said solvent are added. The solvent isallowing Table 5:

TABLE 5.-HOUSEFLY TEST (CONTACT ACTION] Amount of Mortality in peractivecomcent after exposure pound of housefly forapplied in Active compoundmmg./dish 2 hrs. 18 hrs 2i o 1, 000 100 100 II II 100 20 100 (02H 0)i1ss0Ho1-0Ho1i 0 0 (3i) o o 1, 000 100 100 [I n 100 50 100(C2115O)zP-SSCHzCC13 1O 0 40 (C2H O)zi SSO Cl=CHCl (CzH O)2P-SSCH=C c1,

(01) 0 1, 000 100 100 II II 100 0 100 (CH3O)2PSSCHC1CHC12 10 0 (74) 0 01, 000 100 100 l], H 100 0 so (01110): SSCHz-CC13 10 0 40 (84) 0 0 1,000 100 100 1 1 ll 0 90 100 (01330); SSCOI=CHC1 1o 60 100 (91) 0 0 1,000 100 100 II II 0 90 100 (OH;O)2I-SSCH=C on 10 60 100 104 s o 1, 00090 100 H H 100 0 90 (0zH50)iPss0HC10Hc1i 10 0 10 114) s 0 1,000 100 {III 100 10 100 (C2H50)2 SSCHz-C C13 10 0 40 (124) s 0 1,000 ll II 100 o40 (C2H50)2 SSCC1=CHCI 10 60 so (131) s 0 1, 000 90 100 H II 100 0 s0(C2H50)ZPSS CH=CCIZ 10 o 50 (144) 5 1,000 100 100 II II 100 0 40 (CHO)zPS-SCHC1CHC1z l0 0 20 151) s 0 1,000 100 100 II N 100 0 40(CHaO)2PS-SCH2C Cl; 10 0 40 (101) s 0 1,000 100 100 I II 100 10 70(OH;O)zP-SSCC1=CHC1 10 0 30 1 s o 1, 000 100 90 {1 II 100 0 00 01130);-s CH=O 012 10 0 40 NOTE.1 mm.=0.000001 g.

The following further examples are set forth to illuslowed to evaporateleaving a uniform dry film residue. trate, without limitation, theprocess for producing the Ten to twenty flies (Musca domestica) are thenplaced in active compounds according to the present invention: the jarand covered With a screen top. A cotton pad EXAMPLE 6 soaked in a 10%sugar-water solution is placed on top of the screen as food supply. IIII After each of the periods of time stated in the folloW- 70 (CH3O)P sS CHC1CHC1 (145) ing table, the degree of destruction is determined andex- Y Y sulfinyndlthlo' pressed as a percentage: 100% means that all,and 0% Phosphate means that none, of the test creatures are killed. 16.3g. (0.1 mol) of 90% pure 0,0-dimethyl-dithi0 The particular activecompounds tested, the amounts 75 phosphoric acid were dissolved in 100ml. of chloroform.

EXAMPLE 7 0,0-dimethyl-S-(2,2,2-trichloroethyl sulfinyl) thiolphosphate17.5 g. (0.08 mol) 2,2,2-tri-chloroethyl sulfinyl chloride were addeddropwise at 30 C. to 12.5 g. (0.088 mol) 92% 0,0-dimethyl thiophosphatedissolved in 100 ml. CHC1 over a period of one hour. After the addition,the reaction mixture was stirred for three hours and then refluxed forfour hours (until no more HCl evolved). The CHCI solution was washedwith H O, dried over MgSO filtered and stripped, giving 23.9 g. (92%yield) of the stated compound in the form of a light yellow liquid, n1.5205.

EXAMPLE 8 0,0-dimethyl-S-(1,2-dichlorovinyl sulfinyl) dithiophosphate6.75 g. (0.02 mol) 0,0-dimethyl-S-(l,2,2 trichloroethyl sulfinyl)dithiophosphate were dissolved in 100 m1. Skellysolve B and 20.02 g.(0.02 mol) triethylarnine were added at 30 C. The hydrochloride whichformed was filtered after the reaction had reached completion. TheSkellysolve B 1 was stripped giving g. (84% yield) of the statedcompound in the form of a red-brown liquid, n 1.5707.

EXAMPLE 9 0,0-diethyl-S-(2,2-dichlorovinyl sulfinyl) dithiophosphate 9.3g. (0.05 mol) 0,0-diethyl dithiophosphate were dissolved in 100 ml. CHCland 8 g. (0.05 mol) 2,2-dichlorovinyl sulfinyl chloride were added at 30C., allowing HCl to escape. The reaction mixture was refluxed until nomore HCl evolution could be detected, then washed with H O, dried overMgSO filtered and stripped, giving 15.2 g. (100% yield) of the statedcompound in the form of a yellow liquid, n 1.5555.

EXAMPLE 10 0,0-diethyl-S- (2,2-dichlorovinyl sulfinyl thiolpho sphate6.9 g. (0.02 mol) 0,0-diethyl-S-(2,2,2 trichloroethyl sulfinyl)thiophosphate were dissolved in 100 ml. Skellysolve B and 2.02 g. (0.02mol) triethylarnine were added at 30 C. The reaction mixture turned darkas the amine salt was formed. After refluxing for three hours, theSkellysolve B was stripped, the residue dissolved in HCCl washed with HO, dried over MgSO filtered and stripped, giving 4.5 g. (72% yield) ofthe stated compound in the form of a red liquid, 21 1.4914.

Ske1lyso1ve B is commercial hexane of boiling range til-70 C. (143-158"E).

The following compounds are prepared in analogous manner:

(6 CHQO O 0 Light yellow oil.

ll ll yield. r s -CHCl-CHCiz 21mm. CHaO CHzO 0 0 Dark 011.

II II 67% yield. P-S -o o1=orro1 n? mom 01130 01130 O 0 Orange oil.

H 72% yield. P-S- 2 5900 CHaO (25) CzHa Q\fi) (I) 'siieyllow 1031.

a yle P-SSCHCl-CHC1: 2; M100. CzHgO (35) C2H50\(|? (I? ggglow 0 Y 9PsCH2 CCl3 22 5050 C2H5O (45) 021150 0 0 Dark 011- H H 78% yield. 1 s oo1 oHo1 is an CzHsO (15 CHJO S 0 Yellow oil.

H H 83% yield. r s-soH,o on 131.5655 CHaO s i are.

y e 1, PSS-CH=C 01. a; 5520 D CHaO (10 CzH50 S 0 Yellow oil.

ll Quant. yield. PS-SCHClCHClI 2 CzHaO 5) C2H50\fi (I? sligl ltiivfil.

o e P--S-SCH2CCI3 15534; CrHaO (12 021150 S 0 Dark Oil.

[I 70% yield. P-S- -0 01-01101 l 15510- orHsO EXAMPLE 11 Thecorresponding 0,0-din-propyl, isopropyl, -n-butyl, -isobutyl,-sec.-butyl and -tert.-butyl -S-(2,2,2- and 1, 2,2-trichloroethyland2,2- and 1,2-dichlorovinylsulfinyl)- thiol and dithio phosphates may beprepared in analogous manner from the appropriate starting thiol anddithio phosphoric acid esters (II) and sulfinyl chlorides (III) or (IV),as the case may be, such final compounds similarly possessing relativelystrong fungicidal, nematocidal and insecticidal properties.

As examples .of sulfinyl thioland dithio-phosphates of Formula I inwhich R is ethyl or vinyl having three or two chloro substituents,respectively, and X is oxygen or sulfur and R is lower alkyl of 1-4carbon atoms according to the present invention, there may be mentionedin particular:

0,0-di-n-butyl-S-(2,2,2-trichloroethyl sulfinyl)-dithio- QfiiZiethyI-S-(2,2,2-trichloroethyl sulfinyl)-thiolphos- O,1 di:ihyl-S-(1,2,2-trichloroethy1 sulfinyl) -thiolphos- Q-fiiZihyI-S-(2,2,2-trichloroethyl sulfinyl)-thiolphos- O, :t ltir1iethyl-S-( 1,2,2-trichloroethyl sulfinyl) -dithiophos- 190,0-dirnethy1-S-(2,2,2-trichloroethyl sulfinyl)-dithiophosphate,

0,0-diethyl-S-( 1,2,2-trichloroethyl sulfinyl) -dithiophosphate,

0,0-diethy1-S- (2,2,2-trichloroethyl sulfinyl) dithiophosphate,

0,0-di-n-propyl-S-( 1,2,2-trichloroethyl sulfinyl -thiolphosphate,

0,0-diisopropyl-S- 1,2,2-trichloroethyl sulfinyl) -thiolphosphate,

0,0-diisopropyl-S-(2,2,2-trichloroethyl sulfinyl) -thiolphosphate,

0,0-diisopropyl-S-(2,2,Z-trichloroethyl sulfinyl)-dithiophosphate,

0,0-diisopropyl-S-( 1,2,2-trichloroethyl sulfinyl) -dithiophosphate,

0,0-di-n-butyl-S- 2,2,2-trichloroethyl sulfinyl -thiophosphate,

0,0di-n-butyl-S-(2,2,2-trichloroethyl sulfinyl)-dithiophosphate,

0,0-di-n-butyl-S- 1,2,2-trichloroethyl sulfinyl) -dithiophosphate,

0,0-dimethyl-S-( 1,2-dichlorovinyl sulfinyl -thiolphosphate,

0,0-dimethyl-S-(2,2-dichlorovinyl sulfinyl)-thiolphosphate,

0,0-diethyl-S- 1,2-dichloroviny1 sulfinyl) -thiolphosphate,

0,0-diethyl-S- 2,2-dichloroviny1 sulfinyl) -thiolphosphate,

0,0-dimethyl-S-( 1,2-dich1orovinyl sulfinyl) -dithiophosphate,

0,0-dirnethyl-S-(2,2-dichloroviny1 sulfinyl)-dithiophosphate,

0,0-diethyl-S-(2,2-dichloroviny1 sulfinyl) dithiophosphate,

0,0-diethyl-S-( 1,2-dichloroviny1 sulfinyl) -dithiophosphate,

0,0-di-n-propy1-S-(2,2-dichlorovinyl sulfinyl)-dithiophosphate,

0,0-diisopropyl-S-( 1,2-dichloroviny1 sulfinyl) -thiophos phate,

0,0-diisopropyl-S- (2,2-dichlorovinyl sulfinyl) -dithiophosphate,

0,0-di-n-butyl-S-(2,2-dichloroviny1 sulfinyl)dithiophosphate,

0,0-di-n-buty1-S-(1,2-dichloroviny1 sulfinyl)-dithiophosphate,

0,0-di-sec.-buty1-S-( 1,2-dichlorovinyl sulfinyl) -thiolphosphate,

0,0-di-sec.-butyl-S-(2,2-dichlorovinyl sulfinyl)-dithiophosphate,

and the like.

It will be realized by the artisan that all of the foregoing compoundscontemplated by the present invention possess the desired strongpesticidal, especially insecticidal, nematocidal and fungicidal,properties for combating insects, nematodes and fungi, with regard to abroad spectrum of activity, as well as a comparatively low toxicitytoward Warm-blooded creatures, and a concomitantly low phytotoxicity,enabling such compounds to be used with correspondingly favorablecompatibility with warmblooded creatures and higher plants for moreeffective control and/or elimination of insects, nematodes and fungi byapplication of such compounds to such insects, nematodes and fungi and/or their corresponding habitat.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:

1. Sulfinyl thiophosphate of the formula in which R is lower alkyl of1-4 carbon atoms, R is selected from the group consisting oftrichloroethyl and dichlorovinyl, and X is selected from the groupconsisting of oxygen and sulfur.

2. Compound according to claim 1 wherein R is C alkyl, R is selectedfrom the group consisting of 1,2,2- trichloroethyl,2,2,2-trich1oroethyl, 1,2-dichlorovinyl and 2,2-dichlorovinyl, and X isselected from the group consisting of oxygen and sulfur.

3. Compound according to claim 1 wherein R is C alkyl, R is selectedfrom the group consisting of 1,2,2- trichloroethyl and2,2,2-trichloroethyl, and X is selected from the group consisting ofoxygen and sulfur.

4. Compound according to claim 1 wherein R is C alkyl, R is selectedfrom the group consisting of 1,2- dichlorovinyl and 2,2-dichlorovinyl,and X is selected from the group consisting of oxygen and sulfur.

5. Compound according to claim 1 wherein such compound is 0,0-dimethyl-S(2,Z-dichlorovinyl-sulfinyl)-thiolphosphate of the formula 6. Compoundaccording to claim 1 wherein such compound is0,0-dimethyl-S-(1,2,2-trichloroethyl-sulfinyl)-dithiophosphate of theformula 7. Compound according to claim 1 wherein such compound is0,0-dimethyl-S( 1,2-dichlorovinyl-sulfinyl) -thi0lphosphate of theformula 8. Compound according to claim 1 wherein such compound is0,0-diethyl-S-(1,2,2-trichloroethyl-sulfinyl)-dithiophosphate of theformula S II II (CgH5O)gP-SSCHO1CHC13 9. Compound according to claim 1wherein such compound is 0,0-diethyl S (2,2,2-trichloroethy1-sulfinyl)thiol-phosphate of the formula 10. Compound according to claim 1 whereinsuch compound is 0,0diethyl-S- 1,Z-dichlorovinyl-sulfinyl)-thiolphosphate of the formula t I (C HsOhR- S COl=CHCl 11. Compoundaccording to claim 1 wherein such compound is0,0-diethyl-S(2,2,Z-trichloroethyl-sulfinyl)-dithiophosphate of theformula 12. Compound to claim 1 wherein such compound is 0,0-dimethyl S(1,2-dichlorovinyl-sulfinyl)-dithiophosphate of the formula ReferencesCited FOREIGN PATENTS 941,810 11/1963 Great Britain 260-934 CHARLES B.PARKER, Primary Examiner A. H. SUTTO, Assistant Examiner US. Cl. X.R.

."- ,I UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent NO.3629375 Dated December 21, 1971 Inventor(s) Paul C. Aichenegg et a].

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby cerrected as shown below:

Col. 2 line 29 H II J, I

(CH 0 )2 should be V (CH 0 661. 3, line 46 a llowed" should be----'ai1owed Col. 6 line 65 4 7 "product" should be --produce-- Col. 7line 3 7 "gurrgi" shoui d be -=-fung i v Col. 7 line 6 l I 4 to (first oceurrence) shouldbe 'j .n-- Col. 7 line 13 7 '-'there" should be----their- 6 CO1, 10, lines 66 67 7 Lines 66 and 67 should pr Col. 10,'line- 1.

Col. 17, line 37 "20.02". sho l -2 0 UNITED STATES PATENT OFFICE WUnmflcmr: OF CORRECTION Patent No. 3629375 Dzi ted e em ef 421, 1971Inventor(s) Paul C. Aichenegg, et' a1.

It is certified that error appears in the above-idemziified patent andthat said Letters Patent are hereby corrected as shown below:

T- Col. 17 line 41 "B'" should be '-B-- Col. 18 line 10 7.3 hould b --%g7-.

C01. 18 line 14 "n gl'. 59O0" should be g1.509o-- Col. 18 line 17 "nshould be --n Col. 18 line 22 22 v n D hould be n D Col. 18- line 26 "I15" should be n Col. 18 1111530 22 i 2- an... n D should be 11 D C61. 18line 34 "n shou1d be --n "f" 1 Patent No. 3629375 0; 0 Q-- UNITED STATESPATIENT OFFICE CERTIFICATE OF CORRECTION Dated December I 21; 1971Inventor(s) Paul C. Aichenegg, et a1.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

C01. 18 line 37 n D 1 should be n D C01. 18 line 43 H H qp D should be11 D Col. l8, line '46 n 22H- n shoufld be .n D

Signed and sealed this 20th day of Jupe 1972. V

(SEAL) Attest:

ROBERT GOTISCHALK Commissioner of Patents EDWARD MQFLETCHERJR.'Attesting Officer

